WO2008051239A2 - Structures mixtes en nanotubes de carbone mono-paroi et multi-paroi - Google Patents

Structures mixtes en nanotubes de carbone mono-paroi et multi-paroi Download PDF

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WO2008051239A2
WO2008051239A2 PCT/US2006/044846 US2006044846W WO2008051239A2 WO 2008051239 A2 WO2008051239 A2 WO 2008051239A2 US 2006044846 W US2006044846 W US 2006044846W WO 2008051239 A2 WO2008051239 A2 WO 2008051239A2
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carbon nanotubes
nanotubes
walled carbon
walled
carbon
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PCT/US2006/044846
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WO2008051239A9 (fr
WO2008051239A3 (fr
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Jun Ma
Alan Fisher
Robert Hoch
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Hyperion Catalysis International, Inc.
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Priority to CA 2629849 priority Critical patent/CA2629849A1/fr
Priority to EP06851918A priority patent/EP1957406A4/fr
Priority to JP2008541397A priority patent/JP2009515812A/ja
Priority to AU2006349607A priority patent/AU2006349607A1/en
Publication of WO2008051239A2 publication Critical patent/WO2008051239A2/fr
Publication of WO2008051239A9 publication Critical patent/WO2008051239A9/fr
Publication of WO2008051239A3 publication Critical patent/WO2008051239A3/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B1/00—Nanostructures formed by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/168—After-treatment
    • C01B32/174—Derivatisation; Solubilisation; Dispersion in solvents

Definitions

  • the invention relates to carbon nanotube structures containing both single walled and multi walled carbon nanotubes, and methods for preparing same.
  • These carbon nanotube structures include but are not limited to macroscopic two and three dimensional structures of carbon nanotubes such as assemblages, mats, plugs, networks, rigid porous structures, extrudates, etc.
  • the carbon nanotube structures of the present invention have a variety of uses, including but not limited to, porous media for filtration, adsorption, chromatography; electrodes and current collectors for supercapacitors, batteries and fuel cells; catalyst supports, (including electrocatalysis), etc.
  • This invention lies in the field of submicron graphitic carbon fibrils, commonly referred to as nanotubes.
  • Carbon fibrils are vermicular carbon deposits having diameters less than l.O ⁇ , preferably less than 0.5 ⁇ , and even more preferably less than 0.2 ⁇ .
  • Carbon nanotubes can be either multi walled (i.e., have more than one graphene layer more or less parallel to the nanotube axis) or single walled (i.e., have only a single graphene layer parallel to the nanotube axis). Other types of carbon nanotubes are also described below.
  • the carbon nanotubes which can be treated as taught in this application, are distinguishable from commercially available continuous carbon fibers.
  • carbon fibrils In contrast to these fibers which have aspect ratios (L/D) of at least 10 4 and often 10 6 or more, carbon fibrils have desirably large, but unavoidably finite, aspect ratios.
  • the diameter of continuous fibers is also far larger than that of fibrils, being always >1.0 ⁇ and typically 5 to 7 ⁇ .
  • Carbon nanotubes differ physically and chemically from continuous carbon fibers which are commercially available as reinforcement materials, and from other forms of carbon such as standard graphite and carbon black. Standard graphite, because of its structure, can undergo oxidation to almost complete saturation.
  • carbon black is amorphous carbon generally in the form of spheroidal particles having a graphene structure, carbon layers around a disordered nucleus.
  • Carbon nanotubes exist in a variety of forms and have been prepared through the catalytic decomposition of various carbon-containing gases at metal surfaces. Such vermicular carbon deposits have been observed almost since the advent of electron microscopy. (Baker and Harris, Chemistry and Physics of Carbon. Walker and Thrower ed., Vol. 14, 1978, p. 83; Rodriguez, N., J. Mater. Research. Vol. 8, p. 3233 (1993)). [0007] In 1976. Endo et al. (see Oberlin. A. and Endo. M.. J. of Crystal Growth. Vol.
  • the Tennent invention provided access to smaller diameter fibrils, typically 35 to 7O ⁇ A (0.0035 to 0.070 ⁇ ) and to an ordered, "as grown" graphitic surface. Fibrillar carbons of less perfect structure, but also without a pyrolytic carbon outer layer have also been grown.
  • the carbon planes of the graphitic nanotube take on a herring bone appearance. These are termed fishbone fibrils.
  • Geus, U.S. Patent No. 4,855,091 hereby incorporated by reference, provides a procedure for preparation of fishbone fibrils substantially free of a pyrolytic overcoat. These carbon nanotubes are also useful in the practice of the invention.
  • Carbon nanotubes of a morphology similar to the catalytically grown fibrils described above have been grown in a high temperature carbon arc (Iijima, Nature 354, 56, 1991). It is now generally accepted (Weaver, Science 265, 1994; de Heer, Walt A.,
  • Moy disclosed a process for producing hollow, single-walled carbon nanotubes by catalytic decomposition of one or more gaseous carbon compounds by first forming a gas phase mixture carbon feed stock gas comprising one or more gaseous carbon compounds, each having one to six carbon atoms and only H, O, N, S or Cl as hetero atoms, optionally admixed with hydrogen, and a gas phase metal containing compound which is unstable under reaction conditions for said decomposition, and which forms a metal containing catalyst which acts as a decomposition catalyst under reaction conditions; and then conducting said decomposition reaction under decomposition reaction conditions, thereby producing said nanotubes.
  • a gas phase mixture carbon feed stock gas comprising one or more gaseous carbon compounds, each having one to six carbon atoms and only H, O, N, S or Cl as hetero atoms, optionally admixed with hydrogen, and a gas phase metal containing compound which is unstable under reaction conditions for said decomposition, and which forms a metal containing catalyst which acts as a de
  • the invention relates to a gas phase reaction in which a gas phase metal containing compound is introduced into a reaction mixture also containing a gaseous carbon source.
  • the carbon source is typically a Ci through C ⁇ compound having as hetero atoms H, O, N, S or Cl, optionally mixed with hydrogen.
  • Carbon monoxide or carbon monoxide and hydrogen is a preferred carbon feedstock.
  • Increased reaction zone temperatures of approximately 400 0 C to 1300 0 C and pressures of between about 0 and about 100 p.s.i.g., are believed to cause decomposition of the gas phase metal containing compound to a metal containing catalyst. Decomposition may be to the atomic metal or to a partially decomposed intermediate species.
  • the metal containing catalysts (1) catalyze CO decomposition and (2) catalyze SWNT formation.
  • the invention of U.S. Patent No. 6,221,330 may in some embodiments employ an aerosol technique in which aerosols of metal containing catalysts are introduced into the reaction mixture.
  • An advantage of an aerosol method for producing SWNT is that it will be possible to produce catalyst particles of uniform size and scale such a method for efficient and continuous commercial or industrial production. The previously discussed electric arc discharge and laser deposition methods cannot economically be scaled up for such commercial or industrial production.
  • metal containing compounds useful in the invention include metal carbonyls, metal acetyl acetonates, and other materials which under decomposition conditions can be introduced as a vapor which decomposes to form an unsupported metal catalyst.
  • Catalytically active metals include Fe, Co, Mn, Ni and Mo.
  • Molybdenum carbonyls and iron carbonyls are the preferred metal containing compounds which can be decomposed under reaction conditions to form vapor phase catalyst. Solid forms of these metal carbonyls may be delivered to a pretreatment zone where they are vaporized, thereby becoming the vapor phase precursor of the catalyst. It was found that two methods may be employed to form SWNT on unsupported catalysts. [0015] The first method is the direct injection of volatile catalyst. Direct injection of volatile catalyst precursors has been found to result in the formation of SWNT using molybdenum hexacarbonyl [Mo(CO)6] and dicobalt octacarbonyl [CO 2 (CO) 8 ] catalysts.
  • 6,221,330 comprises a quartz thermowell 20 having a seal 24 about 1" from its bottom to form a second compartment.
  • This compartment has two 1/4" holes 26 which are open and exposed to the reactant gases.
  • the catalyst is placed into this compartment, and then vaporized at any desired temperature using a vaporizer furnace 32.
  • This furnace is controlled using a first thermocouple 22.
  • a metal containing compound, preferably a metal carbonyl, is vaporized at a temperature below its decomposition point, reactant gases CO or CO/H 2 sweep the precursor into the reaction zone 34, which is controlled separately by a reaction zone furnace 38 and second thermocouple 42.
  • the metal containing compound is decomposed either partially to an intermediate species or completely to metal atoms. These intermediate species and/or metal atoms coalesce to larger aggregate particles which are the actual catalyst. The particle then grows to the correct size to both catalyze the decomposition of CO and promote SWNT growth.
  • the catalyst particles and the resultant carbon forms are collected on the quartz wool plug 36. Rate of growth of the particles depends on the concentration of the gas phase metal containing intermediate species. This concentration is determined by the vapor pressure (and therefore the temperature) in the vaporizer.
  • the carbon nanotubes are produced therein by contacting a carbon containing gas with metallic catalytic particles.
  • Additional methods of producing single walled carbon nanotubes are disclosed in U.S.S.N. 11/281,571, Zhang, et. al, "Methods For Producing Single Walled Carbon Nanotubes," filed November 16, 2005 and its parent application U.S. Provisional Application No. 60/630,946, filed November 24, 2004, U.S. Provisional Application No. 60/630,781 , filed November 24, 2004 and U.S. Provisional Application No. 60/628,498, filed November 16, 2004. AU of these references are hereby incorporated by reference in their entirety.
  • carbon nanotubes may be in the form of discrete nanotubes, aggregates of nanotubes or both.
  • Nanotubes are prepared as aggregates having various morphologies (as determined by scanning electron microscopy) in which they are randomly entangled with each other to form entangled balls of nanotubes resembling bird nests ("BN"); or as aggregates consisting of bundles of straight to slightly bent or kinked carbon nanotubes having substantially the same relative orientation, and having the appearance of combed yarn ("CY") e.g., the longitudinal axis of each nanotube (despite individual bends or kinks) extends in the same direction as that of the surrounding nanotubes in the bundles; or, as, aggregates consisting of straight to slightly bent or kinked nanotubes which are loosely entangled with each other to form an "open net” (“ON”) structure.
  • CY combed yarn
  • Carbon nanotube structures include assemblages, mats, plugs, networks, rigid porous structures, extrudates, etc.
  • Assemblages are carbon nanotube structures which have relatively uniform properties in along one, preferably two and most desirably three dimensional axis of the three dimensional assemblage.
  • Two dimensionally uniform assemblages take the form of mats.
  • Three dimensionally uniform assemblages may take the form of the container in which they are formed and are typically called plugs.
  • Multi walled carbon nanotube mats may have a thickness between 0.02 and 0.50 millimeters and a density of approximately 0.20 g/cc.
  • assemblages are formed by de-aggregating the carbon nanotube aggregate structure, and then reassembling them to form assemblages.
  • Multi walled carbon nanotube assemblages may have a bulk density of from 0.001 to 0.50 gm/cc and at least two dimensions greater than about 0.02 mm. Assemblages may also have at least two dimensions greater than 0.2 mm.
  • Networks are formed by linking individual functionalized carbon nanotubes together by using a linking molecule between the functionalized groups located on the surface of the carbon nanotubes. (E.g., PCT/US97/03553 or WO 97/32571, hereby incorporated by reference). In general a matlike or pluglike network may have a lower density than the corresponding assemblage, but still within the range of 0.001 to 0.50 g/cc.
  • Rigid porous structures are formed by either linking the individual functionalized carbon nanotubes in an assemblage together without the use of a linking molecule, or by gluing carbon nanotube aggregate structures together with a gluing agent.
  • Rigid porous structures of multi walled carbon nanotubes may have a surface area greater than about 100 m 2 /gm, may be substantially free of micropores and may have a crush strength greater than about 2 lb/in 2 . Rigid porous structures may even have surface area greater than 200 mVgm 2 .
  • Rigid porous structures of multi walled carbon nanotubes may have densities greater than density greater than 0.8 g/cm 3 .
  • Single walled carbon nanotubes typically have smaller diameter than most multi walled carbon nanotubes.
  • structures created from single walled carbon nanotubes will have significantly greater specific surface area (sqm/gm) and lower density than structures created from multi-walled carbon nanotubes ("multi walled carbon nanotube structures").
  • Surface area can be a critical performance parameter for many applications that use carbon nanotubes structures, such as those listed in this application.
  • single walled carbon nanotube structures can have smaller effective pore size than multi walled carbon nanotube structures. Having smaller effective pore size may be beneficial in many applications, and undesirable in other circumstances. For example, smaller pores result in catalyst supports having higher specific surface. Conversely, smaller pores are subject to diffusion limitations and plugging. Thus, the advantages of smaller pore size need to be balanced against other considerations. Parameters, like total porosity, pore size distribution, etc. become important qualifiers of effective pore size.
  • multi walled carbon nanotube assemblages, networks, rigid porous structures and extrudates have specific surface areas between 30 and 600 sqm/gm
  • the corresponding single walled assemblages, networks, structures and extrudates have specific surface areas between 1000 and 2500 sqm/gm.
  • single walled carbon nanotubes are more expensive and less pure than multi walled carbon nanotubes, and are harder to disperse and more difficult to functionalize. As such, multi walled carbon nanotube structures are easier to prepare.
  • the present invention provides carbon nanotube structures containing a mixture of both single walled and multi walled carbon nanotubes.
  • These carbon nanotube structures include but are not limited to macroscopic two and three dimensional structures of carbon nanotubes such as assemblages, mats, plugs, networks, rigid porous structures, extrudates, etc.
  • the carbon nanotube structures of the present invention have a variety of uses, including but not limited to, porous media for filtration, adsorption, chromatography; electrodes and current collectors for supercapacitors, batteries and fuel cells; catalyst supports, (including electrocatalysis), etc.
  • the present invention also provides new methods for creating carbon nanotube structures which contain a mixture of both single walled and multi walled carbon nanotubes.
  • Figure 1 illustrates a schematic diagram of various methods which can be used in an exemplary embodiment to form mixed structure of single-walled and multi-walled carbon nanotubes.
  • Figure 2 which is comprised of Figure 2A and 2B, provides transmission electron micrographs of carbon nanotubes in various stages in accordance with Example 15.
  • nanotube single walled or multiwalled carbon nanotubes.
  • Each refers to an elongated structure preferably having a cross section (e.g., angular fibers having edges) or a diameter (e.g., rounded) less than 1 micron (for multiwalled nanotubes) or less than 5 nm (for single walled nanotubes).
  • nanotube also includes “buckytubes", and fishbone fibrils.
  • Multiwalled nanotubes refers to carbon nanotubes which are substantially cylindrical, graphitic nanotubes of substantially constant diameter and comprise cylindrical graphitic sheets or layers whose c-axes are substantially perpendicular to the cylindrical axis, such as those described, e.g., in U.S. Patent No. 5,171,560 to Tennent, et al.
  • Single walled nanotubes refers to carbon nanotubes which are substantially cylindrical, graphitic nanotubes of substantially constant diameter and comprise a single cylindrical graphitic sheet or layer whose c-axis is substantially perpendicular to their cylindrical axis, such as those described, e.g., in U.S. Patent No.
  • Single walled carbon nanotubes may also be referred to as "SWTs" or “SWNTs”.
  • the term "functional group” refers to groups of atoms that give the compound or substance to which they are linked characteristic chemical and physical properties.
  • a “functionalized” surface refers to a carbon surface on which chemical groups are adsorbed or chemically attached.
  • Grapheme carbon is a form of carbon whose carbon atoms are each linked to three other carbon atoms in an essentially planar layer forming hexagonal fused rings.
  • Graphitic carbon consists of graphenic layers which are essentially parallel to one another and no more than 3.6 angstroms apart.
  • aggregate refers to a dense, microscopic particulate structure comprising entangled carbon nanotubes.
  • micropore refers to a pore which has a diameter of less than 2 nanometers.
  • pores refers to pores having a cross section greater than 2 nanometers and less than 50 nanometers.
  • surface area refers to the total surface area of a substance measurable by the BET technique.
  • accessible surface area refers to that surface area not attributed to micropores (i.e., pores having diameters or cross-sections less than 2 nm).
  • isotropic means that all measurements of a physical property within a plane or volume of the structure, independent of the direction of the measurement, are of a constant value. It is understood that measurements of such non-solid compositions must be taken on a representative sample of the structure so that the average value of the void spaces is taken into account.
  • untreated carbon nanotubes, aggregates or any other carbon nanotube structures mean that that the carbon nanotubes, aggregates, or structures have not been specifically treated with ozone. It does not preclude carbon nanotubes, aggregates, or structures which have been subjected to other non-ozone treatments before the treatment with ozone.
  • the present invention solves the deficiencies of prior carbon nanotube structures by containing both single walled and multi walled carbon nanotubes.
  • Carbon nanotube structures comprising both multi walled and single walled carbon nanotubes can retain the high specific surface area and small effective pore size associated with single walled carbon nanotubes while retaining substantial macroporosity associated with multi walled carbon nanotubes.
  • Multi walled carbon nanotubes also come with a lower cost, and are easier to disperse and functionalize into a carbon nanotube structure.
  • a carbon nanotube structure of the present invention contains multi walled carbon nanotubes to provide the integrity and physical conformation of the structure, and single walled carbon nanotubes to provide the effective surface area. These structures may exhibit a bimodal pore size distribution.
  • the mixed structures have densities between 0.001 and 0.50 g/mL, preferably between 0.05-0.5 g/mL.
  • the mixed structure have surface areas between 300-1800 sqm/g, preferably between 500-1000 sqm/g.
  • the ratio of single walled carbon nanotubes to multi walled carbon nanotubes in the carbon nanotube structure may range from 1/1000 to 1000/1 by weight, or 1/100 to 100/1, or 1/10 to 10/1.
  • the ratio of single walled carbon nanotubes to multi walled carbon nanotubes in the carbon nanotube structure may range from 1/1000 to 100/1 by weight, or 1/10 to 100/1.
  • the ratio of single walled carbon nanotubes to multi walled carbon nanotubes in the carbon nanotube structure may further range from 1/1000 to 10/1 by weight, or 1/100 to 10/1.
  • the ratio of single walled carbon nanotubes to multi walled carbon nanotubes in the carbon nanotube structure range from 1/1000 to 1/1 by weight, or 1/100 to 1/1, or 1/10 to 1/1.
  • the ratio of single walled carbon nanotubes to multi walled carbon nanotubes in the carbon nanotube structure may range from 1/1 to 1000/1 by weight, or 1/1 to 100/1, or 1/1 to 10/1.
  • a carbon nanotube structure is prepared by first dispersing single walled carbon nanotubes aggregates (i.e, disaggregate them into individual tubes if necessary), then adding multi walled carbon nanotubes (also disaggregated into individual tubes if necessary) so as to mix with the single walled carbon nanotubes, and then forming a carbon nanotube structure from the mixture.
  • a three dimensional interpenetrating structure is made via in-situ growth of single-walled nanotubes on the surface of dispersed multi walled nanotube supported catalyst.
  • a highly dispersed Mo carbide catalyst supported on carbon nanotubes have been disclosed in U.S. Patent No. 6,514,897, herein incorporated by reference.
  • Co catalyst can then be deposited on the surface of Mo carbide nanoparticles to construct a catalyst effective for growing single walled carbon nanotubes when exposed to carbon containing reactants at elevated temperatures.
  • metals such as Fe, Co and Ni can be deposited on the surface of single-walled with controlled sizes capable to grow multiwalled nanotubes.
  • the multi walled carbon nanotubes are functionalized and form the structure via the self reaction of functionalized tubes.
  • the multi walled and single walled carbon nanotubes are separately produced and may be separately pretreated before assembling the mixed structure.
  • the multi walled carbon nanotubes may be pre-oxidized so that they can be cross linked and the single walled carbon nanotubes may be pre-loaded with catalyst or catalyst precursor before assembling a supported catalyst structure.
  • mixtures of multi walled and single walled carbon nanotubes can be used to form the carbon nanotube structures of the present invention.
  • a mixture of multi walled carbon nanotubes and single walled carbon nanotubes can be treated with functionalization reagents specific to the multi walled carbon nanotubes.
  • Such a mixture of single and multiwall carbon nanotubes may be formed concomitantly by catalytic growth.
  • Individualized single walled carbon nanotubes generally need to be stabilized by surfactants to avoid reflocculation after dispersion.
  • the multi walled carbon nanotubes can act as a "blocking agent" aiding in preventing such reflocculation.
  • Dispersion of single walled carbon nanotubes can be carried out in polymer, surfactant, micelles and DNA.
  • polymer single walled and multi walled carbon nanotubes can be dispersed via shear generated during melt-processing in a twin screw compounder.
  • liquid processing of single walled carbon nanotubes can also be carried out in polymer, surfactant or micelle to achieve high dispersion before blending with functionalized multiwalled tubes.
  • Single walled carbon nanotubes can be extracted and dispersed in a biological process.
  • DNA-wrapped single walled carbon nanotubes present very high dispersion and purity and can be selectively deposited on a prefunctionalized multiwalled tubes.
  • All combinations of separate and joint dispersion of single walled and multi walled carbon nanotubes, combined with and independent of functionalization are contemplated and included in the scope of the present invention.
  • Figure 1 provides an illustrative schematic diagram of the various methods which can be used to prepare a rigid porous single/multi-walled carbon nanotube structure.
  • a carbon nanotube structure of the present invention is prepared by first creating the structure out of multi walled carbon nanotubes and then use its porosity to capture the single walled carbon nanotubes, for example by flowing a dispersion of single walled carbon nanotubes (appropriately stabilized by surfactant) through the multi walled carbon nanotube structure.
  • the porosity of the multi walled carbon nanotube structure acting as a depth filter, would capture the single walled carbon nanotubes, leading to a mixed structure of high specific area.
  • the single walled carbon nanotubes may be functionalized or otherwise pretreated before being captured by the multi walled carbon nanotube structure.
  • the multi walled carbon nanotube structure can be easily created out of non-functionalized multi walled carbon nanotubes using a binder.
  • a binder with affinity for multi walled carbon nanotubes can be used and the mixed structure assembled out of a mixture of multi walled carbon nanotubes and single walled carbon nanotubes.
  • SWNT single-walled carbon nanotubes
  • CC CC type multi-walled nanotubes
  • MWNT polyvinyl chloride
  • the composite can be digested with ⁇ -butyrolactone to remove all polymer content and the resulting suspension is filtered and calcined at 400 0 C in argon in order to form rigid porous structure containing 25% single-walled and 75% multi- walled nanotubes.
  • Example 2 [0074] 0.1 gram of single-wall and 0.4 gram of CC nanotubes are placed in a 100- mL beaker. 100 grams of isopropanol is then added to the mixture. The mixture is then treated with probe sonicator for 4 hours till forming stable suspension of mostly individualized nanotubes. Then the suspension can be filtered and form a nanotube mat with mixture of single-walled and multi-walled carbon nanotubes (20/80).
  • Example 3 20 gram of carbon nanotubes (CC type) was placed in a 1 -liter round bottom flask and 600 mL concentrated nitric acid (63%) was added to the flask and the temperature was brought up to the reflux condition. The reaction was allowed to proceed for 2 hours and then the system was cooled down to room temperature. The product was subsequently washed thoroughly with deionized water till neutral during filtration. The wet filter cake (Sample A) was set aside for further process.
  • CC type carbon nanotubes
  • sample A The oxidized MWNTs (Sample A) are re-suspended in deionized water to a level of 0.05 wt% and subjected to high shear using a probe sonicator for 1 hour to generate mostly individualized multi-walled nanotubes (Sample C).
  • Example 4 is prepared. To this dispersion of SWNTs is added the oxidized MWNTs, Sample C, and mixed with a Waring blender. The resulting slurry is further subjected to continuous high shear mixing using a probe sonicator for 1 hour to form interpenetrated single-wall and multi-walled nanotube network. The mixture is then concentrated by centrifugation followed by filtration to about 5% total solids. The resulting paste like material in the filter cake is blended in a Retsch mortar mill to a uniform consistency after which it is extruded through a die with a circular aperture forming a strand.
  • the stand is cut to shorter lengths and dried at 200 0 C in air overnight after which it is calcined at 600 0 C in an argon atmosphere for 6 hours to produce rigid particles containing interpenetrating single and multi-walled nanotubes. Ratios of SWNT to MWNT can be controlled by volume of Sample B to C.
  • Example 6 Dry single-walled carbon nanotubes are subject to ozone treatment using the method disclosed in a US Provisional Application 60/621,132, filed October 22, 2004, where functional groups such as carboxyls, hydroxyls, carbonyls, and lactones are more effectively produced on the surface of nanotubes.
  • Ozone is generated via an air purifier made by Del Industry, San Luis Obispo, Calif., which can generate ozone at a rate of 250 mg/hr.
  • a mixture of ozone and air (0.29% ozone) at a flow rate of 1200 mL/min is then passed though a 1-inch (OD) reactor tube packed with dry as-made single-walled nanotubes. The weight of nanotubes before and after ozone treatment are recorded.
  • the reaction is allowed to proceed for a period of 3 to 45 hours at room temperature.
  • the relative amount of acidic groups on the treated sample are measured through titration. 0.25 gram of the sample is placed into a flask containing 300 mL D.I. water and the slurry is titrated with 0.1N NaOH. The consumption of NaOH is translated into the quantity of total surface acidic groups as meq/g. A titer of 2 meq/g is obtained.
  • Example 7 Ozone-treated SWNTs made in Example 6 are individualized using the procedure described in Example 4 to give Sample D. Rigid porous structure of SWNTs and MWNTs can be prepared using Sample C and D as described in Example 5.
  • Example 8 A nanotube mat made of multiwall carbon nanotubes is made by filtration of Sample C followed by cross-linking in argon at 240 0 C.
  • the as-made mat can be used as a trapping medium for collecting single-walled carbon nanotubes.
  • the dispersed single- walled carbon nanotube sample (Sample B) from Example 4 is poured onto the mat placed on a Buchner funnel.
  • the ratio of SWNTs to MWNTs can be controlled by the volume of Sample B and the weight of mat.
  • Example 9 A nanotube mat made of multiwall carbon nanotubes is made by filtration of Sample C followed by cross-linking in argon at 240 0 C.
  • the as-made mat can be used as a trapping medium for collecting single-walled carbon nanotubes.
  • the dispersed single- walled carbon nanotube sample (Sample B) from Example 4 is poured onto the mat placed on a Buchner funnel.
  • the ratio of SWNTs to MWNTs can be controlled
  • a filtering device is set up so both suspension of SWNTs (Sample B) and
  • MWNTs (Sample C) are added to the filter funnel simultaneously.
  • the addition rate is controlled at the ratio of MWNTs to SWNTs at desired value, e.g 1/1 or 5/1, etc.
  • the filtered cake is then freeze-dried at -78°C.
  • the resulting felt contains uniformly distributed single-wall and multiwall nanotubes but has less mechanical strength as compared the product made in Example 5.
  • MWNT can be established via cross-linking of surface oxygenated groups such as carboxyls, hydroxyls, etc. carried out by calcination in inert environment such as argon.
  • the calcination temperature is usually selected between 240 0 C and 600 0 C.
  • Calcined structures exhibit rigid porous nature of multi-walled nanotubes while maintaining high surface area of single-walled nanotubes, e.g. 1000 m 2 /g.
  • residues from carbonizable polymer upon calcination such as polyvinyl chloride, acrylic polymer, phenolic resin, etc., can also be applied to generate such structure.
  • Sample D is further subject to an 8-h reflux with K 2 PtCl 4 in dilute ethylene glycol (3:2 by volume of ethylene glycol to deionized H 2 O) at 120-130 0 C to allow deposition of Pt particles onto the single-walled nanotubes.
  • K 2 PtCl 4 in dilute ethylene glycol (3:2 by volume of ethylene glycol to deionized H 2 O) at 120-130 0 C to allow deposition of Pt particles onto the single-walled nanotubes.
  • K 2 PtCl 4 and 20 mL of diluted ethylene glycol are added per 10 mg of ozone-treated single- walled nanotubes.
  • the product Pt-loaded SWNT bundles
  • deionized water made slightly acidic with a few drops of HCl (a nonoxidizing acid to destabilize the suspension).
  • Typical metal loading of the final material is 10 wt % Pt on SWNTs (Sample E).
  • Deionized water is then added to Sample E to form a uniform suspension and mixed with Sample C made in Example 5 under sonication.
  • the resulting suspension is concentrated using a rotary evaporator, filtered, dried at 120 0 C and calcined in argon at 500 0 C to form a rigid porous structure via cross-linking.
  • the final product is composed of small bundles of single-walled nanotube loaded with 1-2 nm Pt particles locked within a rigid, porous structure formed of multi-walled nanotubes.
  • the Sample made from Example 5 contains interpenetrated single and multi- walled nanotubes with the multi-walled nanotube having primarily hydrophilic surface and the single-walled nanotubes having predominantly hydrophobic surfaces.
  • An amphiphilic block copolymer poly(styrene-block-acrylic acid) (PS-b-PAA) is then dissolved in dimethylformamide, a solvent in which both blocks are well solvated and micelles do not form. With gradual addition of a second solvent such as toluene, the solution forms micelles with quasi-hexagonal arrays of PAA spheres within in a PS matrix.
  • the carboxylic acids groups in the PAA domains can be utilized in an ion-exchange protocol to selectively seize Pd ions.
  • Aqueous solution of Pd(NOs) 2 is added to PS-b-PAA micelles with continuous agitation for 6 hours to allow sufficient ionic exchange.
  • the metal loaded micelles are then blended with the same made from Example 5. After filtration, drying at 120 0 C and calcined in argon at 300 0 C, the sample is further subject to reduction in H 2 at 300 0 C for 1 hour.
  • the product, Sample F shows a metal dispersion of 50% at catalyst loading of 5% with Pd particles preferentially supported on individualized single-walled nanotubes, which are further locked inside a rigid porous structured multi-walled nanotubes.
  • Example 14 [0087] Examples 1 -7 are repeated with SWNTs obtained from Thomas Swan, Ltd.
  • Example 15 A Co-Mo/MgO catalyst was prepared via co-precipitation of Co nitrate and Mg nitrate. 0.1 16 g of Co(NO 3 ).6H 2 O and 2.175 g of Mg(NO 3 ) 2 .6H 2 O were dissolved in 23 mL deionized water in a 100-mL beaker. The molar ratio of Co/Mg was 1/20. 20 g of 0.1% Ammonium hepta-molybdate solution was then added into the mixed solution of Co(NOa) 2 & Mg(NOs) 2 and the solution was kept under constant agitation. Approximately 3 g of 30% NH 4 OH was then added to precipitate Co and Mg concurrently.
  • Figure 2A showed the product after a catalyst exposed to ethylene and hydrogen at 700 0 C for a short period of time, e.g. 2 minutes. Metal nanoparticles of 1-1.5 nm were observed coated on the surface of multi- walled nanotubes with diameter of approximately 10 nm.
  • Figure 2B showed that, without being exposed to air, the in-situ formed metal nanoparticles supported on multi-walled carbon nanotubes can further grow single-walled carbon nanotubes of 1-1.5 nm. That is, Figure 2B showed the product after reaction with CO at 800 0 C for 15 minutes immediately after 2A. These tubes are either in the form of small bundles containing three to five tubes or individualized as single tubes.
  • multi-walled nanotubes has already formed a three dimension network with metal nanoparticles of approximately 1 nm size coated on their surface. Subsequently contacting carbonaceous reactant under conditions ripe for single-walled nanotube formation, these in-situ generated metal catalyst nanoparticles can further generate single-wall nanotubes, which are mostly in the form of thin bundles (3-4 tubes) or individualized.
  • the composition of nanotube mixture can be easily controlled by altering the duration of two separate reactions.
  • SWNT-growing catalyst can also be pre-deposited on MWNTs (CC-type) ex- situ.
  • Carbon nanotube-supported MOO3 and Mo 2 C nanoparticles can be prepared using the procedure described in US Patent 6,514,897. A sample of these materials is prepared with initial C/Mo ratio of 20. Iron, cobalt species or combination thereof is then added to this sample via impregnation of metal nitrate aqueous solution with desired concentration.
  • 0.674 gram of Fe(NO 3 ) 3 .9H 2 O and 0.485 gram of Co(NO 3 ) 2 .6H 2 O are added to 5 gram of the M0 2 C/MWNT sample followed by calcination in air at 250 0 C.
  • Example 17 A slurry of the 20 grams of ozone-treated SWNTs from Example 6, 8 grams of a gamma alumina (available from Degussa as Oxide C) and 100-mL of deionized water was made up in a multi-neck, 250 mL indented flask with rapid stirring. The pH of the slurry was adjusted to 6.0. A solution I was made by mixing 0.52 g of ammonium molybdate [(NH 4 )6M ⁇ 7 ⁇ 24 .4H 2 O], dissolved in 5 mL of deionized water and 1.5 grams of 41% ferric nitrate [Fe(NOs) 3 ] solution (9.5% Fe).
  • Solution I and a 20% by weight ammonium carbonate solution were added concurrently with rapid mixing to maintain the pH at 6.0.+-.0.5.
  • the pH was controlled by the relative rates of addition of Solution I and Solution II.
  • a silicone defoamer ANTIFOAM 289 available from Sigma chemical was added in 5-300 ppm to suppress foaming during precipitation. The addition took about one hour, after which the resulting slurry was vacuum filtered using Number 50 Whatman filter paper.
  • the filter cake was washed thoroughly twice by reslurrying in portions in a Waring blender for two minutes at medium speed with a total volume of 100 mL of deionized water followed by vacuum filtering.
  • the filter cake was dried at 162°C in a convection oven overnight. Samples were ground to -100 mesh and tested for productivity.
  • the tube reactor was quickly heated to 680 0 C in an Argon stream to purge the reactor after which the gas stream was switched to a mixture of hydrogen and ethylene at a flow rate of 400 and 200 mL/min under standard conditions.
  • the reactor was maintained at temperature for the about 20 minutes, after which the reactor was cooled in argon and emptied.
  • the yield based on catalyst is 7 and the yield based on iron content is 140.
  • the ratio of SWNTs to MWNTs is approximately 1/10.

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Abstract

L'invention concerne des structures en nanotubes de carbone contenant à la fois des nanotubes de carbone mono-paroi et multi-paroi, ainsi que des procédés pour leur préparation. Ces structures en nanotubes de carbone comprennent, mais ne se limitent pas à : des structures macroscopiques bi- et tridimensionnelles en nanotubes de carbone telles que des assemblages, des nappes, des plots, des réseaux, des structures poreuses rigides, des extrudats, etc. Les structures en nanotubes de carbone de la présente invention conviennent à diverses utilisations, notamment de façon non limitative : des milieux poreux destinés à la filtration, l'adsorption, la chromatographie ; des électrodes et des collecteurs de courant destinés à des super-condensateurs, des batteries et des piles à combustible ; des supports de catalyseurs (y compris pour l'électrocatalyse), etc.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012512811A (ja) * 2008-12-19 2012-06-07 デザインド・ナノチューブス・リミテッド・ライアビリティ・カンパニー 剥離したカーボンナノチューブ、その製造方法およびそれから得られる生成物
US9422413B1 (en) 2010-12-14 2016-08-23 Molecular Rebar Design, Llc Elastomer formulations comprising discrete carbon nanotube fibers
US9475921B2 (en) 2011-06-23 2016-10-25 Molecular Rebar Design, Llc Nanoplate-nanotube composites, methods for production thereof and products obtained therefrom
US9997785B2 (en) 2011-06-23 2018-06-12 Molecular Rebar Design, Llc Nanoplate-nanotube composites, methods for production thereof and products obtained therefrom

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DK1831440T3 (da) * 2004-11-16 2010-11-08 Hyperion Catalysis Int Fremgangsmåder til fremstilling af katalysatorer understøttet på carbonnanorørnetværk
AU2006349607A1 (en) * 2005-11-16 2008-05-02 Hyperion Catalysis International, Inc. Mixed structures of single walled and multi walled carbon nanotubes
JP4062346B2 (ja) * 2006-08-17 2008-03-19 富士ゼロックス株式会社 カーボンナノチューブ膜およびその製造方法、並びにそれを用いたキャパシタ
US8628746B2 (en) * 2007-04-12 2014-01-14 Raytheon Company System and method for dispersing nanostructures in a composite material
US8491292B1 (en) 2007-07-31 2013-07-23 Raytheon Company Aligning nanomaterial in a nanomaterial composite
US8636972B1 (en) * 2007-07-31 2014-01-28 Raytheon Company Making a nanomaterial composite
CN101409338A (zh) * 2007-10-10 2009-04-15 清华大学 锂离子电池负极,其制备方法和应用该负极的锂离子电池
EP2973786B1 (fr) 2013-03-15 2023-03-01 Wellstat BioCatalysis, LLC Procédés de fabrication d'électrodes à nanofibres pour batteries
EP2827412A1 (fr) * 2013-07-16 2015-01-21 DWI an der RWTH Aachen e.V. Microtubes constitués de nanotubes de carbone
JP2016190772A (ja) * 2015-03-31 2016-11-10 日本ゼオン株式会社 炭素膜およびその製造方法
CN109399611A (zh) * 2017-08-16 2019-03-01 东北林业大学 一种碳纳米管的制备方法
KR102377623B1 (ko) * 2018-01-29 2022-03-24 주식회사 엘지화학 탄소나노튜브 분산액의 제조방법
US11471789B2 (en) * 2018-07-12 2022-10-18 Abb Schweiz Ag Material phase with electrical lead
TWI783231B (zh) * 2019-05-31 2022-11-11 美商美國琳得科股份有限公司 多壁、少壁、及單壁奈米碳管混合物的薄膜
JP6841318B2 (ja) * 2019-12-16 2021-03-10 日本ゼオン株式会社 炭素膜およびその製造方法

Family Cites Families (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5171560A (en) * 1984-12-06 1992-12-15 Hyperion Catalysis International Carbon fibrils, method for producing same, and encapsulated catalyst
US5707916A (en) * 1984-12-06 1998-01-13 Hyperion Catalysis International, Inc. Carbon fibrils
US5165909A (en) * 1984-12-06 1992-11-24 Hyperion Catalysis Int'l., Inc. Carbon fibrils and method for producing same
US4663230A (en) * 1984-12-06 1987-05-05 Hyperion Catalysis International, Inc. Carbon fibrils, method for producing same and compositions containing same
US6375917B1 (en) * 1984-12-06 2002-04-23 Hyperion Catalysis International, Inc. Apparatus for the production of carbon fibrils by catalysis and methods thereof
US4855091A (en) * 1985-04-15 1989-08-08 The Dow Chemical Company Method for the preparation of carbon filaments
ZA907803B (en) * 1989-09-28 1991-07-31 Hyperion Catalysis Int Electrochemical cells and preparing carbon fibrils
US5569635A (en) * 1994-05-22 1996-10-29 Hyperion Catalysts, Int'l., Inc. Catalyst supports, supported catalysts and methods of making and using the same
JPH07507961A (ja) * 1992-05-22 1995-09-07 ハイピリオン カタリシス インターナショナル インコーポレイテッド 炭素原繊維の製造方法及びそれに用いられる触媒
IL109497A (en) * 1993-05-05 1998-02-22 Hyperion Catalysis Int Three-dimensional macroscopic clusters of randomly arranged charcoal fibrils and products containing these
US5424054A (en) * 1993-05-21 1995-06-13 International Business Machines Corporation Carbon fibers and method for their production
US6203814B1 (en) * 1994-12-08 2001-03-20 Hyperion Catalysis International, Inc. Method of making functionalized nanotubes
US5800706A (en) * 1996-03-06 1998-09-01 Hyperion Catalysis International, Inc. Nanofiber packed beds having enhanced fluid flow characteristics
IL126976A (en) * 1996-05-15 2001-11-25 Hyperion Catalysis Internat Nano-fibers are made of graphite in electrochemical capacitors
CA2254970C (fr) * 1996-05-15 2007-10-02 Hyperion Catalysis International, Inc. Structures de carbone poreuses et rigides, leurs procedes de fabrication et d'utilisation et produits les contenant
US6683783B1 (en) * 1997-03-07 2004-01-27 William Marsh Rice University Carbon fibers formed from single-wall carbon nanotubes
US6221330B1 (en) * 1997-08-04 2001-04-24 Hyperion Catalysis International Inc. Process for producing single wall nanotubes using unsupported metal catalysts
US6630772B1 (en) * 1998-09-21 2003-10-07 Agere Systems Inc. Device comprising carbon nanotube field emitter structure and process for forming device
CA2350099C (fr) * 1998-11-03 2008-05-20 William Marsh Rice University Nucleation en phase gazeuse et croissance de nanotubes de carbone a paroi simple a partir de co haute pression
US6514897B1 (en) * 1999-01-12 2003-02-04 Hyperion Catalysis International, Inc. Carbide and oxycarbide based compositions, rigid porous structures including the same, methods of making and using the same
US6333016B1 (en) * 1999-06-02 2001-12-25 The Board Of Regents Of The University Of Oklahoma Method of producing carbon nanotubes
US6495258B1 (en) * 2000-09-20 2002-12-17 Auburn University Structures with high number density of carbon nanotubes and 3-dimensional distribution
US6872681B2 (en) * 2001-05-18 2005-03-29 Hyperion Catalysis International, Inc. Modification of nanotubes oxidation with peroxygen compounds
US6706402B2 (en) * 2001-07-25 2004-03-16 Nantero, Inc. Nanotube films and articles
US7259410B2 (en) * 2001-07-25 2007-08-21 Nantero, Inc. Devices having horizontally-disposed nanofabric articles and methods of making the same
JP2006508636A (ja) * 2002-05-08 2006-03-16 ザ・ボード・オブ・トラスティーズ・オブ・ザ・レランド・スタンフォード・ジュニア・ユニバーシティ コンジットの配列を有するナノチューブマット
DE60321371D1 (de) * 2002-10-15 2008-07-10 Agfa Graphics Nv Polymer für wärmeempfindlichen vorläufer einer lithographischen druckplatte
US7419601B2 (en) * 2003-03-07 2008-09-02 Seldon Technologies, Llc Nanomesh article and method of using the same for purifying fluids
JP4380282B2 (ja) * 2003-09-26 2009-12-09 富士ゼロックス株式会社 カーボンナノチューブ複合構造体の製造方法
US7374685B2 (en) * 2003-12-18 2008-05-20 Clemson University Process for separating metallic from semiconducting single-walled carbon nanotubes
US7641829B2 (en) * 2004-07-21 2010-01-05 Florida State University Research Foundation Method for mechanically chopping carbon nanotube and nanoscale fibrous materials
CA2584433A1 (fr) * 2004-10-22 2006-12-21 Hyperion Catalysis International, Inc. Ozonolyse amelioree de nanotubes de carbone
CA2588111A1 (fr) * 2004-11-16 2006-05-26 Hyperion Catalysis International, Inc. Procede pour preparer des nanotubes de carbone a paroi simple
DK1831440T3 (da) * 2004-11-16 2010-11-08 Hyperion Catalysis Int Fremgangsmåder til fremstilling af katalysatorer understøttet på carbonnanorørnetværk
EP1827681A4 (fr) * 2004-11-17 2011-05-11 Hyperion Catalysis Int Methodes pour preparer des supports catalytiques et des catalyseurs a support a partir de nanotubes en carbone a paroi unique
AU2006349607A1 (en) * 2005-11-16 2008-05-02 Hyperion Catalysis International, Inc. Mixed structures of single walled and multi walled carbon nanotubes
KR100745736B1 (ko) * 2006-02-23 2007-08-02 삼성에스디아이 주식회사 카본나노튜브, 이를 포함한 담지 촉매 및 상기 담지 촉매를이용한 연료전지

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of EP1957406A4 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012512811A (ja) * 2008-12-19 2012-06-07 デザインド・ナノチューブス・リミテッド・ライアビリティ・カンパニー 剥離したカーボンナノチューブ、その製造方法およびそれから得られる生成物
JP2014237583A (ja) * 2008-12-19 2014-12-18 モレキュラー レバー デザイン エルエルシー 剥離したカーボンナノチューブ、その製造方法およびそれから得られる生成物
KR101748190B1 (ko) * 2008-12-19 2017-06-16 몰레큘라 레바 디자인 엘엘씨 박리된 탄소 나노튜브, 이의 제조 방법 및 이로부터 수득된 제품
US10361450B2 (en) 2008-12-19 2019-07-23 Designed Nanotubes, LLC Exfoliated carbon nanotubes, methods for production thereof and products obtained therefrom
US9422413B1 (en) 2010-12-14 2016-08-23 Molecular Rebar Design, Llc Elastomer formulations comprising discrete carbon nanotube fibers
US9493626B1 (en) 2010-12-14 2016-11-15 Molecular Rebar Design, Llc Dispersions comprising discrete carbon nanotube fibers
US9636649B2 (en) 2010-12-14 2017-05-02 Molecular Rebar Design, Llc Dispersions comprising discrete carbon nanotube fibers
US9475921B2 (en) 2011-06-23 2016-10-25 Molecular Rebar Design, Llc Nanoplate-nanotube composites, methods for production thereof and products obtained therefrom
US9997785B2 (en) 2011-06-23 2018-06-12 Molecular Rebar Design, Llc Nanoplate-nanotube composites, methods for production thereof and products obtained therefrom

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